U.S. patent number 7,799,855 [Application Number 10/957,799] was granted by the patent office on 2010-09-21 for flame retardant thermoplastic polycarbonate compositions, use and method thereof.
This patent grant is currently assigned to Sabic Innovative Plastics IP B.V.. Invention is credited to Thomas Ebeling, Monica Martinez Marugan, Srinivas Siripurapu.
United States Patent |
7,799,855 |
Ebeling , et al. |
September 21, 2010 |
Flame retardant thermoplastic polycarbonate compositions, use and
method thereof
Abstract
A thermoplastic composition contains about 20 to about 90 wt. %
of a polycarbonate resin; up to about 35 wt. % of an impact
modifier; about 0.5 to about 30 wt. % of a
polysiloxane-polycarbonate copolymer; and about 0.5 to about 20 wt.
% of a phosphorus-containing flame retardant, each based on the
total combined weight of the thermoplastic composition, exclusive
of any filler. An article of manufacture having a wall having a
thickness of 3 mm or less may be made using the composition, e.g.,
by molding, extruding, or shaping the above-described composition
into an article. Alternatively, an article may be made by
ultrasonically welding a first part comprising the foregoing
composition a second part.
Inventors: |
Ebeling; Thomas (Evansville,
IN), Marugan; Monica Martinez (Bergen op Zoom,
NL), Siripurapu; Srinivas (Evansville, IN) |
Assignee: |
Sabic Innovative Plastics IP
B.V. (NL)
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Family
ID: |
35589492 |
Appl.
No.: |
10/957,799 |
Filed: |
October 4, 2004 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20060074156 A1 |
Apr 6, 2006 |
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US 20080227896 A9 |
Sep 18, 2008 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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10015049 |
Nov 12, 2001 |
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Current U.S.
Class: |
524/127; 524/140;
524/141 |
Current CPC
Class: |
C08L
69/00 (20130101); C08L 83/10 (20130101); C08L
69/00 (20130101); C08L 83/00 (20130101); C08L
69/00 (20130101); C08L 2666/02 (20130101); C08L
83/10 (20130101); C08L 2666/14 (20130101); C08L
51/04 (20130101); C08L 23/0884 (20130101); C08K
5/49 (20130101); C08L 51/085 (20130101); C08L
25/12 (20130101); C08L 53/02 (20130101); C08L
23/16 (20130101); C08L 55/02 (20130101) |
Current International
Class: |
C08K
5/523 (20060101) |
Field of
Search: |
;524/127,140-141 |
References Cited
[Referenced By]
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WO |
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WO |
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WO |
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WO |
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WO |
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WO 2005/075549 |
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Other References
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strength of their coalescence seams". Publication Date Dec. 30,
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EP0247430A2. "Flame-retarding thermoplastic moulding composition"
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EP0248308A2. "Moulding compunds with easy mould releasability".
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cocondensates with siloxanes and with elastomeric polymerisation
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copolymer, for good mechanical properties". Publication Date: Nov.
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Primary Examiner: Szekely; Peter
Attorney, Agent or Firm: Cantor Colburn LLP
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a Continuation-In-Part of, and claims the
benefit of, U.S. utility application entitled, "FLAME RETARDANT
RESINOUS COMPOSITIONS AND METHOD" having Ser. No. 10/015,049, filed
Nov. 12, 2001 now abandoned.
Claims
What is claimed is:
1. A thermoplastic composition, consisting essentially of: about 40
to about 80 wt. % of a polycarbonate resin; about 2 to about 15 wt.
% of an impact modifier; about 10 to about 25 wt. % of a
polysiloxane-polycarbonate copolymer comprising
polydiorganosiloxane blocks of formula (6): ##STR00014## wherein
each R is independently a C.sub.1-13 monovalent organic radical and
D has an average value of about 40 to about 60; an anti-drip agent;
and about 0.5 to about 20 wt. % of a phosphorus-containing flame
retardant, each based on the total combined weight of the
thermoplastic composition, exclusive of any filler; wherein a
one-eighth inch (3.18 mm) (.+-.3%) bar comprising the thermoplastic
composition has a notched Izod impact strength of at least about
3.6 ft-lb/inch determined in accordance with ASTM D256 at room
temperature; and wherein a sample of the thermoplastic composition
having a thickness of about 2.0 mm achieves a UL94 5VB rating in
the absence of a brominated and/or chlorinated flame retardant.
2. The composition of claim 1 wherein a sample of the thermoplastic
composition having a thickness of about 2.0 mm to about 0.1 mm,
when exposed to an open flame, has a flame out time of less than 10
seconds and with no dripping with a probability of first time pass
of at least 0.85, in the absence of a brominated and/or chlorinated
flame retardant.
3. The composition of claim 1, wherein a sample of the
thermoplastic composition having a thickness of about 1.5 mm
achieves a UL94 5VB rating in the absence of a brominated and/or
chlorinated flame retardant.
4. The composition of claim 1, wherein a sample of the
thermoplastic composition having a thickness of about 1.2 mm
achieves a UL94 5VB rating in the absence of a brominated and/or
chlorinated flame retardant.
5. The composition of claim 1, wherein a sample of the
thermoplastic composition having a thickness of about 2.0 mm to
about 0.1 mm, when exposed to an open flame, has a flame out time
of less than 30 seconds in the absence of a brominated and/or
chlorinated flame retardant.
6. The composition of claim 5, wherein the sample has a flame out
time of less than 30 seconds without dripping.
7. The composition of claim 6 wherein the sample has a flame out
time of less than 10 seconds.
8. The composition of claim 1 wherein a sample of the thermoplastic
composition having a thickness of about 2.0 mm to about 0.1 mm,
when exposed to an open flame, has a flame out time of less than 10
seconds and with no dripping with a probability of first time pass
of at least 0.85, in the absence of a brominated and/or chlorinated
flame retardant.
9. The composition of claim 8 wherein the sample has a thickness of
about 0.1 mm to about 1.5 mm.
10. The composition of claim 9 wherein the sample has a thickness
of about 0.8 mm to about 1.5 mm.
11. The composition of claim 1 comprising more than 5 wt %
polysiloxane-polycarbonate copolymer.
12. The composition of claim 1 comprising about 17.5 to about 25
wt. % polysiloxane-polycarbonate copolymer.
13. The composition of claim 1, having a melt viscosity at
260.degree. C./1500 sec.sup.-1 of about 50 to about 500
Pascal-second, measured in accordance with ISO 11443.
14. The composition of claim 13 wherein a sample of the
thermoplastic composition having a thickness of about 0.1 to about
2.0 mm achieves a UL94 V2 rating in the absence of a brominated
and/or chlorinated flame retardant.
15. The composition of claim 13, wherein a sample of the
thermoplastic composition having a thickness of about 0.1 mm to
about 2.0 mm achieves a UL94 V1 rating in the absence of a
brominated and/or chlorinated flame retardant.
16. The composition of claim 13, wherein a sample of the
thermoplastic composition having a thickness of about 0.1 mm to
about 2.0 mm achieves a UL94 V0 rating in the absence of a
brominated and/or chlorinated flame retardant.
17. The composition of claim 1, wherein a sample of the
thermoplastic composition having a thickness of about 0.1 mm to
about 2.0 mm achieves a UL94 V1 rating in the absence of a
brominated and/or chlorinated flame retardant.
18. The composition of claim 1, wherein a sample of the
thermoplastic composition having a thickness of about 0.1 mm to
about 2.0 mm achieves a UL94 V0 rating in the absence of a
brominated and/or chlorinated flame retardant.
19. The composition of claim 1, wherein a sample of the
thermoplastic composition having a thickness of about 1.2 mm to
about 2.0 mm achieves a UL94 5 VB rating in the absence of a
brominated and/or chlorinated flame retardant.
20. The composition of claim 1 wherein a one-eighth inch (3.18 mm)
(.+-.3%) bar comprising the composition has a notched Izod impact
strength of at least about 6 ft-lb/inch determined in accordance
with ASTM D256 at room temperature.
21. The composition of claim 1, wherein the
polysiloxane-polycarbonate copolymer comprises aromatic carbonate
units of formula (1): ##STR00015## wherein at least about 60
percent of the total number of R.sup.1 groups are aromatic organic
radicals and the balance thereof are aliphatic, alicyclic, or
aromatic radicals; and polydiorganosiloxane units of formula (7)
##STR00016## wherein each R is independently a C.sub.1-13
monovalent organic radical; D has an average value of about 40 to
about 60; each R.sup.2 is independently a divalent C.sub.2-C.sub.8
aliphatic group; each M is independently a halogen, cyano, nitro,
C.sub.1-C.sub.8 alkylthio, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8
alkoxy, C.sub.2-C.sub.8 alkenyl, C.sub.2-C.sub.8 alkenyloxy group,
C.sub.3-C.sub.8 cycloalkyl, C.sub.3-C.sub.8 cycloalkoxy,
C.sub.6-C.sub.10 aryl, C.sub.6-C.sub.10 aryloxy, C.sub.7-C.sub.12
aralkyl, C.sub.7-C.sub.12 aralkoxy, C.sub.7-C.sub.12 alkaryl, or
C.sub.7-C.sub.12 alkaryloxy; and each n is independently 0, 1, 2,
3, or 4.
22. The composition of claim 21, wherein R.sup.1 is a divalent
radical of formula (2): ##STR00017## wherein each of A.sup.1 and
A.sup.2 is a monocyclic divalent aryl radical and Y.sup.1 is a
bridging radical having one or two atoms that separates A.sup.1
from A.sup.2; each R is independently a C.sub.1-C.sub.13 alkyl,
C.sub.1-C.sub.13 alkoxy, C.sub.2-C.sub.13 alkenyl, C.sub.2-C.sub.13
alkenyloxy, C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6
cycloalkoxy, C.sub.6-C.sub.10 aryl, C.sub.6-C.sub.10 aryloxy,
C.sub.7-C.sub.13 aralkyl, C.sub.7-C.sub.13 aralkoxy,
C.sub.7-C.sub.13 alkaryl, or a C.sub.7-C.sub.13 alkaryloxy, each
R.sup.2 is independently a C.sub.1-C.sub.3 alkylene, each M is
independently, and each n is 1.
23. The composition of claim 22, wherein each Y.sup.1 is
independently --O--, --S--, --S(O)--, --S(O.sub.2)--, --C(O)--,
methylene, cyclohexyl-methylene, 2-[2.2.1]-bicycloheptylidene,
ethylidene, isopropylidene, neopentylidene, cyclohexylidene,
cyclopentadecylidene, cyclododecylidene, or adamantylidene; each R
is independently a C.sub.1-8 alkyl, trifluoropropyl, C.sub.1 -8
cyanoalkyl, phenyl, chlorophenyl, or tolyl group; each M is a
methyl, ethyl, propyl, methoxy, ethoxy, propoxy, phenyl,
chlorophenyl, or tolyl group; R.sup.2 is a trimethylene group; and
R is a C.sub.1-8 alkyl, trifluoropropyl, C.sub.1-8 cyanoalkyl,
phenyl, chlorophenyl, or tolyl.
24. The composition of claim 23 wherein A.sup.1 and A.sup.2 are
each a divalent phenyl group; Y.sup.1 is methylene,
cyclohexylidene, or isopropylidene; M is methoxy; and R is methyl,
or a mixture of methyl and trifluoropropyl, or a mixture of methyl
and phenyl.
25. The composition of claim 1, further comprising a thermoplastic
polymer having a Tg of greater than about 20.degree. C., and
comprising units derived from a monovinyl aromatic compound,
itaconic acid, acrylamide, N-substituted acrylamide methacrylamide,
maleic anhydride, maleimide, N-alkyl, aryl or haloaryl substituted
maleimide, a glycidyl (meth)acrylate, a monomer of the general
formula (12): ##STR00018## wherein R is hydrogen, C.sub.1-C.sub.5
alkyl, bromo, or chloro and X.sup.c is cyano, C.sub.1-C.sub.12
alkoxycarbonyl, or C.sub.1-C.sub.12 aryloxycarbonyl, or a
combination comprising at least one of the foregoing monomers.
26. The composition of claim 1, further comprising a thermoplastic
polymer having a Tg of greater than about 20.degree. C., and
comprising units derived from styrene, 3-methylstyrene,
3,5-diethylstyrene, 4-n-propylstyrene, alpha-methylstyrene,
alpha-methyl vinyltoluene, alpha-chloro styrene,
alpha-bromostyrene, dichlorostyrene, dibromostyrene, tetra -chloro
styrene, acrylonitrile, ethacrylonitrile, methacrylonitrile,
alpha-chloroacrylonitrile, beta -chloroacrylonitrile,
alpha-bromoacrylonitrile, methyl acrylate, methylmethacrylate,
ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, propyl
acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, or a
combination comprising at least one of the foregoing monomers.
27. The composition of claim 1, wherein the impact modifier
comprises an acrylic impact modifier, an ASA impact modifier, a
diene impact modifier, an organosiloxane impact modifier, an
organosiloxane-branched acrylate impact modifier, an EPDM impact
modifier, a styrene-butadiene-styrene impact modifier, a
styrene-ethylene-butadiene-styrene impact modifier, an ABS impact
modifier, an MBS impact modifier, a glycidyl ester impact modifier,
or a combination comprising at least one of the foregoing impact
modifiers.
28. An article comprising the composition of claim 1 and having a
wall having a thickness of 3 mm or less.
29. A method for forming an article, comprising molding, extruding
or shaping the composition of claim 1 to form the article having a
wall having a thickness of 3 mm or less.
30. The method of claim 29 further comprising ultrasonically
welding the article to a polymeric part.
31. A method for making an article comprising ultrasonically
welding a first part comprising a composition according to claim 1
to a second part.
32. The method of claim 31 wherein the second part comprises a
composition according to claim 1.
33. An article comprising a first part comprising a composition
according to claim 1 ultrasonically welded to a second part.
34. The article of claim 33 wherein the second part comprises a
composition according to claim 1.
Description
BACKGROUND OF THE INVENTION
This disclosure relates to thermoplastic polycarbonate
compositions, and in particular to flame retardant thermoplastic
polycarbonate compositions, methods of manufacture, and use
thereof.
Polycarbonates are useful in the manufacture of articles and
components for a wide range of applications, from automotive parts
to electronic appliances. Because of their broad use, particularly
in electronic applications, it is desirable to provide
polycarbonates with flame retardancy. Many known flame retardant
agents used with polycarbonates contain bromine and/or chlorine.
Brominated and/or chlorinated flame retardant agents are less
desirable because impurities and/or by-products arising from these
agents can corrode the equipment associated with manufacture and
use of the polycarbonates. Brominated and/or chlorinated flame
retardant agents are also increasingly subject to regulatory
restriction.
Nonhalogenated flame retardants have been proposed for
polycarbonates, including various fillers, phosphorus-containing
compounds, and certain salts. It has been difficult to meet the
strictest standards of flame retardancy using the foregoing flame
retardants, however, without also using brominated and/or
chlorinated flame retardants, particularly in thin samples. In
addition, non-brominated and/or non-chlorinated flame retardants
can adversely affect desirable physical properties of the
polycarbonate compositions, particularly impact strength.
Polysiloxane-polycarbonate copolymers have also been proposed for
use as non-brominated and non-chlorinated flame retardants. For
example, U.S. Application Publication No. 2003/015226 to Cella
discloses a polysiloxane-modified polycarbonate comprising
polysiloxane units and polycarbonate units, wherein the
polysiloxane segments comprise 1 to 20 polysiloxane units. Use of
other polysiloxane-modified polycarbonates are described in U.S.
Pat. No. 5,380,795 to Gosens, U.S. Pat. No. 4,746,701 to Kress et
al., U.S. Pat. No. 5,488,086 to Umeda et al., and EP 0 692 522B1 to
Nodera, et al., for example.
While the foregoing flame retardants are suitable for their
intended purposes, there nonetheless remains a continuing desire in
the industry for continued improvement in flame retardance,
including a need for polycarbonate compositions having improved
flame retardance without use of brominated and/or chlorinated flame
retardants. It would also be advantageous if improved flame
retardance could be achieved without substantial degradation of
properties such as impact strength.
BRIEF SUMMARY OF THE INVENTION
A thermoplastic composition comprises about 20 to about 90 wt. % of
a polycarbonate resin; up to about 35 wt. % of an impact modifier;
about 0.5 to about 30 wt. % of a polysiloxane-polycarbonate
copolymer; and about 0.5 to about 20 wt. % of a
phosphorus-containing flame retardant, each based on the total
combined weight of the thermoplastic composition, exclusive of any
filler.
In yet another embodiment, an article comprises the above-described
composition and has a wall having a thickness of 3 mm or less.
In still another embodiment, a method of manufacture of an article
comprises molding, extruding, or shaping the above-described
composition into an article having a wall having a thickness of 3
mm or less.
In another aspect, a method for making an article comprising
ultrasonically welding a first part comprising a composition as
described herein to a second part.
According to another aspect, an article comprises a first part
comprising a composition as described herein ultrasonically welded
to a second part.
The above described and other features are exemplified by the
following figures and detailed description.
BRIEF DESCRIPTION OF THE FIGURES
Referring now to the figures, which are exemplary embodiments, and
wherein the like elements are numbered alike:
FIG. 1 is a flow chart illustrating the UL Audit/Follow-up Services
Process;
FIG. 2 shows a distribution curve for burn time data obtained from
a typical UL-94 flame test, in comparison with a distribution curve
for a logarithmic transformation of the data;
FIG. 3 is a graph showing a relationship between time to drip
performance and the content of polysiloxane-polycarbonate copolymer
in compositions as described herein;
FIG. 4 is a graph showing a relationship between flame out time
performance and the content of polysiloxane-polycarbonate copolymer
in compositions as described herein; and
FIG. 5 is an exploded schematic perspective view of a test article
comprising parts ultrasonically welded together.
DETAILED DESCRIPTION OF THE INVENTION
Disclosed herein are thermoplastic polycarbonate compositions
having improved flame retardance, including flame resistance
performance characteristics such as flame out time (FOT) and time
to drip (TTD). Without being bound by theory, it is believed that
the favorable results obtained herein are obtained by careful
balancing of the relative amounts of a polycarbonate as specified
below and a polysiloxane-polycarbonate copolymer as specified
below, in combination with other components such as an organic
phosphorus-containing flame retardant and, optionally, an impact
modifier, as specified below. In another advantageous feature, the
melt viscosity of the compositions can be adjusted so as to provide
a thin article with improved flame retardance and good physical
properties.
As used herein, the terms "polycarbonate" and "polycarbonate resin"
means compositions having repeating structural carbonate units of
the formula (1):
##STR00001## in which at least about 60 percent of the total number
of R.sup.1 groups are aromatic organic radicals and the balance
thereof are aliphatic, alicyclic, or aromatic radicals. Preferably,
each R.sup.1 is an aromatic organic radical and, more preferably, a
radical of the formula (2):
##STR00002## wherein each of A.sup.1 and A.sup.2 is a monocyclic
divalent aryl radical and Y' is a bridging radical having one or
two atoms that separate A.sup.1 from A.sup.2. In an exemplary
embodiment, one atom separates A.sup.1 from A.sup.2. Illustrative
non-limiting examples of radicals of this type are --O--, --S--,
--S(O)--, --S(O.sub.2)--, --C(O)--, methylene, cyclohexylmethylene,
2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene,
neopentylidene, cyclohexylidene, cyclopentadecylidene,
cyclododecylidene, and adamantylidene. The bridging radical Y.sup.1
is preferably a hydrocarbon group or a saturated hydrocarbon group
such as methylene, cyclohexylidene, or isopropylidene.
Polycarbonates can be produced by the interfacial reaction of
dihydroxy compounds having the formula HO--R.sup.1--OH, which
includes dihydroxy compounds of formula (3):
##STR00003## wherein Y.sup.1, A.sup.1 and A.sup.2 are as described
above. Also included are bisphenol compounds of general formula
(4):
##STR00004## wherein R.sup.a and R.sup.b each represent a halogen
atom or a monovalent hydrocarbon group and may be the same or
different; p and q are each independently integers from 0 to 4; and
X.sup.a represents one of the groups of formula (5):
##STR00005## wherein R.sup.c and R.sup.d each independently
represent a hydrogen atom or a monovalent linear or cyclic
hydrocarbon group and R.sup.e is a divalent hydrocarbon group.
Some illustrative, non-limiting examples of suitable dihydroxy
compounds include the dihydroxy-substituted hydrocarbons disclosed
by name or formula (generic or specific) in U.S. Pat. No.
4,217,438. A nonexclusive list of specific examples of suitable
dihydroxy compounds includes the following: resorcinol,
4-bromoresorcinol, hydroquinone, 4,4'-dihydroxybiphenyl,
1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,
bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane,
bis(4-hydroxyphenyl)-1-naphthylmethane,
1,2-bis(4-hydroxyphenyl)ethane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,
bis(4-hydroxyphenyl)phenylmethane,
2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis
(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)isobutene,
1,1-bis(4-hydroxyphenyl)cyclododecane,
trans-2,3-bis(4-hydroxyphenyl)-2-butene,
2,2-bis(4-hydroxyphenyl)adamantine,
(alpha,alpha'-bis(4-hydroxyphenyl)toluene,
bis(4-hydroxyphenyl)acetonitrile,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-ethyl-4-hydroxyphenyl)propane,
2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,
2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,
2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,
2,2-bis(3-allyl-4-hydroxyphenyl)propane,
2,2-bis(3-methoxy-4-hydroxyphenyl)propane,
2,2-bis(4-hydroxyphenyl)hexafluoropropane,
1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,
1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,
1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,
4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,
1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol
bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,
bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,
bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine,
2,7-dihydroxypyrene,
6,6'-dihydroxy-3,3,3',3'-tetramethylspiro(bis)indane
("spirobiindane bisphenol"), 3,3-bis(4-hydroxyphenyl)phthalide,
2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,
2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,
3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and
2,7-dihydroxycarbazole, and the like, as well as mixtures
comprising at least one of the foregoing dihydroxy compounds.
A nonexclusive list of specific examples of the types of bisphenol
compounds that may be represented by formula (3) includes
1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane (hereinafter "bisphenol A" or
"BPA"), 2,2-bis(4-hydroxyphenyl)butane,
2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)n-butane,
2,2-bis(4-hydroxy-1-methylphenyl)propane, and
1,1-bis(4-hydroxy-t-butylphenyl)propane. Combinations comprising at
least one of the foregoing dihydroxy compounds may also be
used.
It is also possible to employ two or more different dihydroxy
compounds or a copolymer of a dihydroxy compounds with a glycol or
with a hydroxy- or acid-terminated polyester or with a dibasic acid
or hydroxy acid in the event a carbonate copolymer rather than a
homopolymer is desired for use. Polyarylates and
polyester-carbonate resins or their blends can also be employed.
Branched polycarbonates are also useful, as well as blends of
linear polycarbonate and a branched polycarbonate. The branched
polycarbonates may be prepared by adding a branching agent during
polymerization.
These branching agents are well known, and include polyfunctional
organic compounds containing at least three functional groups
selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl,
and mixtures thereof. Specific examples include trimellitic acid,
trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy
phenyl ethane, isatin-bis-phenol, tris-phenol TC
(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA
(4(4(1,1-bis(p-hydroxyphenyl)-ethyl)alpha,alpha-dimethyl
benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid,
and benzophenone tetracarboxylic acid. The branching agents may be
added at a level of about 0.05-2.0 weight percent. Branching agents
and procedures for making branched polycarbonates are described in
U.S. Pat. Nos. 3,635,895 and 4,001,184, which are incorporated by
reference. All types of polycarbonate end groups are contemplated
as being useful in the thermoplastic composition.
Preferred polycarbonates are based on bisphenol A, in which each of
A.sup.1 and A.sup.2 is p-phenylene and Y.sup.1 is isopropylidene.
Preferably, the average molecular weight of the polycarbonate is
about 5,000 to about 100,000, more preferably about 10,000 to about
65,000, and most preferably about 15,000 to about 35,000.
In one embodiment, the polycarbonate has flow properties suitable
for the manufacture of thin articles. Melt volume flow rate (often
abbreviated MVR) measures the rate of extrusion of a thermoplastics
through an orifice at a prescribed temperature and load.
Polycarbonates suitable for the formation of flame retardant
articles may have an MVR, measured at 260.degree. C./2.16 Kg, of
about 4 to about 30 grams per centimeter cubed (g/cm.sup.3).
Polycarbonates having an MVR under these conditions of about 12 to
about 30, specifically about 15 to about 30 g/cm.sup.3 may be
useful for the manufacture of articles having thin walls. Mixtures
of polycarbonates of different flow properties may be used to
achieve the overall desired flow property.
Methods for the preparation of polycarbonates by interfacial
polymerization are well known. Although the reaction conditions of
the preparative processes may vary, several of the preferred
processes typically involve dissolving or dispersing the dihydric
phenol reactant in aqueous caustic soda or potash, adding the
resulting mixture to a suitable water immiscible solvent medium and
contacting the reactants with the carbonate precursor, such as
phosgene, in the presence of a suitable catalyst such as
triethylamine or a phase transfer catalyst, and under controlled pH
conditions, e.g., about 8 to about 10. The most commonly used water
immiscible solvents include methylene chloride, 1,2-dichloroethane,
chlorobenzene, toluene, and the like.
Among the preferred phase transfer catalysts that can be used are
catalysts of the formula (R.sup.3).sub.4Q.sup.+X, wherein each R3
is the same or different, and is a C.sub.1-10 alkyl group; Q is a
nitrogen or phosphorus atom; and X is a halogen atom or a C.sub.1-8
alkoxy group or C.sub.6-188 aryloxy group. Suitable phase transfer
catalysts include, for example, [CH.sub.3(CH.sub.2).sub.3].sub.4NX,
[CH.sub.3(CH.sub.2).sub.3].sub.4PX,
[CH.sub.3(CH.sub.2).sub.5].sub.4NX,
[CH.sub.3(CH.sub.2).sub.6].sub.4NX,
[CH.sub.3(CH.sub.2).sub.4].sub.4NX,
CH.sub.3[CH.sub.3(CH.sub.2).sub.3].sub.3NX,
CH.sub.3[CH.sub.3(CH.sub.2).sub.2].sub.3NX wherein X is Cl.sup.-,
Br.sup.- or--a C.sub.1-8 alkoxy group or C.sub.6-188 aryloxy group.
An effective amount of a phase transfer catalyst may be about 0.1
to about 10 wt. %, about 0.5 to about 2 wt. % based on the weight
of bisphenol in the phosgenation mixture.
Alternatively, melt processes may be used. A catalyst may be used
to accelerate the rate of polymerization of the dihydroxy
reactant(s) with the carbonate precursor. Representative catalysts
include but are not limited to tertiary amines such as
triethylamine, quaternary phosphonium compounds, quaternary
ammonium compounds, basic alkali metal salts, basic alkali earth
metal salts, and the like.
Alternatively, polycarbonates may be prepared by co-reacting, in a
molten state, the dihydroxy reactant(s) and a diaryl carbonate
ester, such as diphenyl carbonate, in the presence of a
transesterification catalyst in a Banbury mixer, twin screw
extruder, or the like to form a uniform dispersion. Volatile
monohydric phenol is removed from the molten reactants by
distillation and the polymer is isolated as a molten residue.
The polycarbonates can be made in a wide variety of batch,
semi-batch or continuous reactors. Such reactors are, for example,
stirred tank, agitated column, tube, and recirculating loop
reactors. Recovery of the polycarbonate can be achieved by any
means known in the art such as through the use of an anti-solvent,
steam precipitation or a combination of anti-solvent and steam
precipitation.
The polysiloxane-polycarbonate copolymers comprise polycarbonate
blocks and polydiorganosiloxane blocks. The polycarbonate blocks
comprise repeating structural units of formula (1) as described
above, and preferably wherein R.sup.1 is of formula (2) as
described above. These units may be derived from reaction of
dihydroxy compounds of formula (3) as described above. In one
embodiment, the dihydroxy compound is bisphenol A, in which each of
A.sup.1 and A.sup.2 is p-phenylene and Y.sup.1 is
isopropylidene.
The polydiorganosiloxane blocks comprise repeating structural units
of formula (6):
##STR00006## wherein each occurrence of R is same or different, and
is a C.sub.1-13 monovalent organic radical. For example, R may be a
C.sub.1-C.sub.13 alkyl group, C.sub.1-C.sub.13 alkoxy group,
C.sub.2-C.sub.13 alkenyl group, C.sub.2-C.sub.13 alkenyloxy group,
C.sub.3-C.sub.6 cycloalkyl group, C.sub.3-C.sub.6 cycloalkoxy
group, C.sub.6-C.sub.10 aryl group, C.sub.6-C.sub.10 aryloxy group,
C.sub.7-C.sub.13 aralkyl group, C.sub.7-C.sub.13 aralkoxy group,
C.sub.7-C.sub.13 alkaryl group, or C.sub.7-C.sub.13 alkaryloxy
group. Combinations of the foregoing R groups may be used in the
same copolymer.
D in formula (6) is selected so as to provide an effective level of
flame retardance to the thermoplastic composition. The value of D
will therefore vary depending on the type and relative amount of
each component in the thermoplastic composition, including the type
and amount of polycarbonate, impact modifier,
polysiloxane-polycarbonate copolymer, and other flame retardants.
Suitable values for D may be determined by one of ordinary skill in
the art without undue experimentation using the guidelines taught
herein. Generally, D has an average value of 2 to about 1000,
specifically about 10 to about 100, more specifically about 25 to
about 75. In one embodiment, D has an average value of about 40 to
about 60, and in still another embodiment, D has an average value
of about 50. Where D is of a lower value, e.g., less than about 40,
it may be necessary to use a relatively larger amount of the
polysiloxane-polycarbonate copolymer. Conversely, where D is of a
higher value, e.g., greater than about 40, it may be necessary to
use a relatively smaller amount of the polysiloxane-polycarbonate
copolymer.
In one embodiment the polydiorganosiloxane blocks comprise
repeating structural units of formula (7):
##STR00007## wherein R and D are as defined above.
R.sup.2 in formula (7) is a divalent C.sub.2-C.sub.8 aliphatic
group. Each M in formula (7) may be the same or different, and may
be a halogen, cyano, nitro, C.sub.1-C.sub.8 alkylthio,
C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, C.sub.2-C.sub.8
alkenyl, C.sub.2-C.sub.8 alkenyloxy group, C.sub.3-C.sub.8
cycloalkyl, C.sub.3-C.sub.8 cycloalkoxy, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 aryloxy, C.sub.7-C.sub.12 aralkyl,
C.sub.7-C.sub.12 aralkoxy, C.sub.7-C.sub.12 alkaryl, or
C.sub.7-C.sub.12 alkaryloxy, wherein each n is independently 0, 1,
2, 3, or 4.
In one embodiment, M is bromo or chloro, an alkyl group such as
methyl, ethyl, or propyl, an alkoxy group such as methoxy, ethoxy,
or propoxy, or an aryl group such as phenyl, chlorophenyl, or
tolyl; R.sup.2 is a dimethylene, trimethylene or tetramethylene
group; and R is a C.sub.1-8 alkyl, haloalkyl such as
trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl
or tolyl. In another embodiment, R is methyl, or a mixture of
methyl and trifluoropropyl, or a mixture of methyl and phenyl. In
still another embodiment, M is methoxy, n is one, R.sup.2 is a
divalent C.sub.1-C.sub.3 aliphatic group, and R is methyl.
These units may be derived from the corresponding dihydroxy
polydiorganosiloxane (8):
##STR00008## wherein R, D, M, R.sup.2, and n are as described
above.
Such dihydroxy polysiloxanes can be made by effecting a platinum
catalyzed addition between a siloxane hydride of the formula
(9):
##STR00009## wherein R and D are as previously defined, and an
aliphatically unsaturated monohydric phenol. Suitable aliphatically
unsaturated monohydric phenols included, for example, eugenol,
2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol,
4-allyl-2-bromophenol, 4-allyl-2-t-butoxyphenol,
4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol,
2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol,
2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6-dimethylphenol.
Mixtures comprising at least one of the foregoing may also be
used.
The polysiloxane-polycarbonate copolymer may be manufactured by
reaction of dihydroxy polysiloxane (8) with a carbonate source and
a dihydroxy aromatic compound of formula (3), optionally in the
presence of a phase transfer catalyst as described above. Suitable
conditions are similar to those useful in forming polycarbonates.
Preferably, the copolymers are prepared by phosgenation, at
temperatures from below 0.degree. C. to about 100.degree. C.,
preferably about 25.degree. C. to about 50.degree. C. Since the
reaction is exothermic, the rate of phosgene addition may be used
to control the reaction temperature. The amount of phosgene
required will generally depend upon the amount of the dihydric
reactants. Alternatively, the polysiloxane-polycarbonate copolymers
may be prepared by co-reacting in a molten state, the dihydroxy
monomers and a diaryl carbonate ester, such as diphenyl carbonate,
in the presence of a transesterification catalyst as described
above.
In the production of the polysiloxane-polycarbonate copolymer, the
amount of dihydroxy polydiorganosiloxane is selected so as to
provide an effective level of flame retardance to the thermoplastic
composition. The amount of dihydroxy polydiorganosiloxane will
therefore vary depending on desired level of flame retardancy, the
value of D, and the type and relative amount of each component in
the thermoplastic composition, including the type and amount of
polycarbonate, type and amount of impact modifier, type and amount
of polysiloxane-polycarbonate copolymer, and type and amount of
other flame retardants. Suitable amounts of dihydroxy
polydiorganosiloxane can be determined by one of ordinary skill in
the art without undue experimentation using the guidelines taught
herein. The amount of dihydroxy polydiorganosiloxane may be
selected so as to produce a copolymer comprising about 0.1 to about
40 wt. %, for example, about 8 to about 40 wt. % of
polydimethylsiloxane, or an equivalent molar amount of another
polydiorganosiloxane. In one embodiment, the amount of dihydroxy
polydiorganosiloxane may be selected to produce a copolymer
comprising about 15 to about 30 wt. % of polydimethylsiloxane, or
an equivalent molar amount of another polydiorganosiloxane. The
amount of dimethylsiloxane units in the polysiloxane-polycarbonate
copolymer may be determined by those of ordinary skill in the art
using known methods. For example, the weight percent of
dimethylsiloxane units in a compound of formula (8) may be
determined by comparison of the integrated intensity of the
aromatic protons to the protons on the siloxane chains in the
.sup.1H NMR spectra of a homogenous sample dissolved in CDCl.sub.3
(without tetramethylsilane).
The polysiloxane-polycarbonate copolymers have a weight-average
molecular weight (Mw, measured, for example, by gel permeation
chromatography, ultra-centrifugation, or light scattering) of about
10,000 to about 200,000, preferably about 20,000 to about
100,000.
The polycarbonate composition may further include an impact
modifier composition comprising a particular combination of impact
modifiers to increase its impact resistance. Suitable impact
modifiers may be an elastomer-modified graft copolymer comprising
(i) an elastomeric (i.e., rubbery) polymer substrate having a Tg
below 0.degree. C., more specifically about -40.degree. to
-80.degree. C., and (ii) a rigid polymeric superstrate grafted to
the elastomeric polymer substrate. As is known, elastomer-modified
graft copolymers may be prepared by first providing an elastomeric
polymeric backbone. At least one grafting monomer, and preferably
two, are then polymerized in the presence of the polymer backbone
to obtain the graft copolymer.
Depending on the amount of elastomer-modified polymer present, a
separate matrix or continuous phase of ungrafted rigid polymer or
copolymer may be simultaneously obtained along with the
elastomer-modified graft copolymer. Typically, such impact
modifiers comprise about 40 to about 95 wt. % elastomer-modified
graft copolymer and about 5 to about 65 wt. % graft (co)polymer,
based on the total weight of the impact modifier. In another
embodiment, such impact modifiers comprise about 50 to about 85 wt.
%, more specifically about 75 to about 85 wt. % rubber-modified
graft copolymer, together with about 15 to about 50 wt. %, more
specifically about 15 to about 25 wt. % graft (co)polymer, based on
the total weight of the impact modifier. The ungrafted rigid
polymers or copolymers may also be separately prepared, for example
by radical polymerization, in particular by emulsion, suspension,
solution or bulk polymerization, and added to the impact modifier
composition or polycarbonate composition. Such ungrafted rigid
polymers or copolymers preferably have number average molecular
weights of from 20,000 to 200,000.
Suitable materials for use as the elastomeric polymer backbone
include, for example, conjugated diene rubbers; copolymers of a
conjugated diene with less than about 50 wt. % of a copolymerizable
monomer; C.sub.1-8 alkyl (meth)acrylate elastomers; olefin rubbers
such as ethylene propylene copolymers (EPR) or
ethylene-propylene-diene monomers (EPDM); silicone rubbers;
elastomeric C.sub.1-8 alkyl (meth)acrylates; elastomeric copolymers
of C.sub.1-8 alkyl(meth)acrylates with butadiene and/or styrene; or
combinations comprising at least one of the foregoing
elastomers.
Suitable conjugated diene monomers for preparing the elastomer
backbone are of formula (10):
##STR00010## wherein each X.sup.b is independently hydrogen,
C.sub.1-C.sub.5 alkyl, or the like. Examples of conjugated diene
monomers that may be used are butadiene, isoprene, 1,3-heptadiene,
methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene,
2-ethyl-1,3-pentadiene; 1,3- and 2,4-hexadienes, and the like, as
well as mixtures comprising at least one of the foregoing
conjugated diene monomers. Specific conjugated diene homopolymers
include polybutadiene and polyisoprene.
Copolymers of a conjugated diene rubber may also be used, for
example those produced by aqueous radical emulsion polymerization
of a conjugated diene and one or more monomers copolyrnerizable
therewith. Monomers that are suitable for copolymerization with the
conjugated diene include monovinylaromatic monomers containing
condensed aromatic ring structures, such as vinyl naphthalene,
vinyl anthracene and the like, and monomers of formula (11):
##STR00011## wherein each X.sup.c is independently hydrogen,
C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl,
C.sub.6-C.sub.12 aryl, C.sub.7-C.sub.12 aralkyl, C.sub.7-C.sub.12
alkaryl, C.sub.1-C.sub.12 alkoxy, C.sub.3-C.sub.12 cycloalkoxy,
C.sub.6-C.sub.12 aryloxy, chloro, bromo, or hydroxy, and R is
hydrogen, C.sub.1-C.sub.5 alkyl, bromo, or chloro. Examples of the
suitable monovinylaromatic monomers that may be used include
styrene, 3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene,
alpha-methylstyrene, alpha-methyl vinyltoluene,
alpha-chlorostyrene, alpha-bromostyrene, dichlorostyrene,
dibromostyrene, tetra-chlorostyrene, combinations comprising at
least one of the foregoing compounds, and the like. Styrene and/or
alpha-methylstyrene are commonly used as monomers copolymerizable
with the conjugated diene monomer. Mixtures of the foregoing
monovinyl monomers and monovinylaromatic monomers may also be
used.
Other monomers that may be copolymerized with the conjugated diene
are monovinylic monomers such as itaconic acid, acrylamide,
N-substituted acrylamide or methacrylamide, maleic anhydride,
maleimide, N-alkyl, aryl or haloaryl substituted maleimide,
glycidyl (meth)acrylates, and monomers of the general formula
(12):
##STR00012## wherein R is as previously defined and X.sup.c is
cyano, C.sub.1-C.sub.12 alkoxycarbonyl, C.sub.1-C.sub.12
aryloxycarbonyl, or the like. Examples of monomers of formula (12)
include acrylonitrile, ethacrylonitrile, methacrylonitrile,
alpha-chloroacrylonitrile, beta-chloroacrylonitrile,
alpha-bromoacrylonitrile, methyl acrylate, methyl methacrylate,
ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, propyl
acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, combinations
comprising at least one of the foregoing monomers, and the like.
Monomers such as n-butyl acrylate, ethyl acrylate, and 2-ethylhexyl
acrylate are commonly used as monomers copolymerizable with the
conjugated diene monomer.
Suitable (meth)acrylate rubbers suitable for use as the elastomeric
polymer backbone may be cross-linked, particulate emulsion
homopolymers or copolymers of C.sub.1-8 alkyl (meth)acrylates, in
particular C.sub.4-6 alkyl acrylates, optionally in admixture with
up to 15 wt. % of comonomers such as styrene, methyl methacrylate,
butadiene, isoprene, vinyl methyl ether or acrylonitrile, and
mixtures comprising at least one of the foregoing comonomers.
Optionally, up to 5 wt. % a polyfunctional crosslinking comonomer
may be present, for example divinylbenzene, alkylenediol
di(meth)acrylates such as glycol bisacrylate, alkylenetriol
tri(meth)acrylates, polyester di(meth)acrylates, bisacrylamides,
triallyl cyanurate, triallyl isocyanurate, allyl(meth)acrylate,
diallyl maleate, diallyl fumarate, diallyl adipate, triallyl esters
of citric acid, triallyl esters of phosphoric acid, and the like,
as well as combinations comprising at least one of the foregoing
crosslinking agents.
The elastomeric polymer substrate may be in the form of either a
block or random copolymer. The particle size of the substrate is
not critical, for example, an average particle size of 0.05 to 8
micrometers, more specifically 0.1 to 1.2 micrometers, still more
specifically 0.2 to 0.8 micrometers, for emulsion based polymerized
rubber lattices or 0.5 to 10 microns, preferably 0.6 to 1.5
microns, for mass polymerized rubber substrates which also have
included grafted monomer occlusions. Particle size may be measured
by simple light transmission methods or capillary hydrodynamic
chromatography (CHDF). The rubber substrate may be a particulate,
moderately cross-linked conjugated diene or C.sub.4-6 alkyl
acrylate rubber, and preferably has a gel content greater than 70%.
Also suitable are mixtures of conjugated diene and C.sub.4-6 alkyl
acrylate rubbers.
In the preparation the elastomeric graft copolymer, the elastomeric
polymer backbone may comprise about 40 to about 95 wt. % of the
total graft copolymer, more specifically about 50 to about 85 wt.
%, and even more specifically about 75 to about 85 wt. % of the
elastomer-modified graft copolymer, the remainder being the rigid
graft phase.
The elastomer-modified graft polymers may be polymerized by mass,
emulsion, suspension, solution or combined processes such as
bulk-suspension, emulsion-bulk, bulk-solution or other techniques,
using continuous, semibatch, or batch processes.
In one embodiment, the elastomer-modified graft polymer may be
obtained by graft polymerization of a mixture comprising a
monovinylaromatic monomer and optionally one or more comonomers in
the presence of one or more elastomeric polymer substrates. The
above-described monovinylaromatic monomers may be used in the rigid
graft phase, including styrene, alpha-methyl styrene, halostyrenes
such as dibromostyrene, vinyltoluene, vinylxylene, butylstyrene,
para-hydroxystyrene, methoxystyrene, or combinations comprising at
least one of the foregoing monovinylaromatic monomers. The
monovinylaromatic monomers may be used in combination with one or
more comonomers, for example the above-described monovinylic
monomers and/or monomers of the general formula (12). In one
specific embodiment, the monovinylaromatic monomer is styrene or
alpha-methyl styrene, and the comonomer is acrylonitrile, ethyl
acrylate, and/or methyl methacrylate. In another specific
embodiment, the rigid graft phase may be a copolymer of styrene and
acrylonitrile, a copolymer of alpha-methylstyrene and
acrylonitrile, or a methyl methacrylate homopolymer or copolymer.
Specific examples of such elastomer-modified graft copolymers
include but are not limited to acrylonitrile-butadiene-styrene
(ABS), acrylonitrile-styrene-butyl acrylate (ASA), methyl
methacrylate-acrylonitrile-butadiene-styrene (MABS), and methyl
methacrylate-butadiene-styrene (MBS), and
acrylonitrile-ethylene-propylene-diene-styrene (AES).
Acrylonitrile-butadiene-styrene graft copolymers are well known in
the art and many are commercially available, including, for
example, the high-rubber acrylonitrile-butadiene-styrene resins
available from General Electric Company as BLENDEX.RTM. grades 131,
336, 338, 360, and 415.
In another embodiment the impact modifier has a core-shell
structure wherein the core is an elastomeric polymer substrate and
the shell is a rigid thermoplastic polymer that is readily wet by
the polycarbonate. The shell may merely physically encapsulate the
core, or the shell may be partially or essentially completely
grafted to the core. More specifically, the shell comprises the
polymerization product of a monovinylaromatic compound and/or a
monovinylic monomer or an alkyl(meth)acrylate.
An example of a suitable impact modifier of this type may be
prepared by emulsion polymerization and is free of basic materials
such as alkali metal salts of C.sub.6-30 fatty acids, for example
sodium stearate, lithium stearate, sodium oleate, potassium oleate,
and the like, alkali metal carbonates, amines such as dodecyl
dimethyl amine, dodecyl amine, and the like, and ammonium salts of
amines. Such materials are commonly used as surfactants in emulsion
polymerization, and may catalyze transesterification and/or
degradation of polycarbonates. Instead, ionic sulfate, sulfonate,
or phosphate surfactants may be used in preparing the impact
modifiers, particularly the elastomeric substrate portion of the
impact modifiers. Suitable surfactants include, for example,
C.sub.1-22 alkyl or C.sub.7-25 alkylaryl sulfonates, C.sub.1-22
alkyl or C.sub.7-25 alkylaryl sulfates, C.sub.1-22 alkyl or
C.sub.7-25 alkylaryl phosphates, substituted silicates, and
mixtures thereof. A specific surfactant is a C.sub.6-16,
specifically a C.sub.8-12 alkyl sulfonate. This emulsion
polymerization process is described and disclosed in various
patents and literature of such companies as Rohm & Haas and
General Electric Company. In the practice, any of the
above-described impact modifiers may be used providing it is free
of the alkali metal salts of fatty acids, alkali metal carbonates,
and other basic materials. A specific impact modifier of this type
is an MBS impact modifier wherein the butadiene substrate is
prepared using above-described sulfonates, sulfates, or phosphates
as surfactants. It is also preferred that the impact modifier have
a pH of about 3 to about 8, specifically about 4 to about 7.
Another specific type of elastomer-modified impact modifier
composition comprises structural units derived from: at least one
silicone rubber monomer, a branched acrylate rubber monomer having
the formula H.sub.2C.dbd.C(R.sup.d)C(O)OCH.sub.2CH.sub.2R.sup.e,
wherein R.sup.d is hydrogen or a C.sub.1-C.sub.8 linear or branched
hydrocarbyl group and R.sup.e is a branched C.sub.3-C.sub.16
hydrocarbyl group; a first graft link monomer; a polymerizable
alkenyl-containing organic material; and a second graft link
monomer. The silicone rubber monomer may comprise, for example, a
cyclic siloxane, tetraalkoxysilane, trialkoxysilane,
(acryloxy)alkoxysilane, (mercaptoalkyl)alkoxysilane,
vinylalkoxysilane, or allylalkoxysilane, alone or in combination,
e.g., decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
trimethyltriphenylcyclotrisiloxane,
tetramethyltetraphenylcyclotetrasiloxane,
tetramethyltetravinylcyclotetrasiloxane,
octaphenylcyclotetrasiloxane, octamethylcyclotetrasiloxane and/or
tetraethoxysilane.
Exemplary branched acrylate rubber monomers include iso-octyl
acrylate, 6-methyloctyl acrylate, 7-methyloctyl acrylate,
6-methylheptyl acrylate, and the like, alone or in combination. The
polymerizable alkenyl-containing organic material may be, for
example, a monomer of formula (11) or (12), e.g., styrene,
alpha-methylstyrene, acrylonitrile, methacrylonitrile, or an
unbranched (meth)acrylate such as methyl methacrylate, 2-ethylhexyl
methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate,
or the like, alone or in combination.
The at least one first graft link monomer may be an
(acryloxy)alkoxysilane, a (mercaptoalkyl)alkoxysilane, a
vinylalkoxysilane, or an allylalkoxysilane, alone or in
combination, e.g.,
(gamma-methacryloxypropyl)(dimethoxy)methylsilane and/or
(3-mercaptopropyl)trimethoxysilane. The at least one second graft
link monomer is a polyethylenically unsaturated compound having at
least one allyl group, such as allyl methacrylate, triallyl
cyanurate, or triallyl isocyanurate, alone or in combination.
The silicone-acrylate impact modifier compositions can be prepared
by emulsion polymerization, wherein, for example at least one
silicone rubber monomer is reacted with at least one first graft
link monomer at a temperature from about 30.degree. C. to about
110.degree. C. to form a silicone rubber latex, in the presence of
a surfactant such as dodecylbenzenesulfonic acid. Alternatively, a
cyclic siloxane such as cyclooctamethyltetrasiloxane and a
tetraethoxyorthosilicate may be reacted with a first graft link
monomer such as (gamma-methacryloxypropyl)methyldimethoxysilane, to
afford silicone rubber having an average particle size from about
100 nanometers to about 2 microns. At least one branched acrylate
rubber monomer is then polymerized with the silicone rubber
particles, optionally in presence of a cross linking monomer, such
as allylmethacrylate in the presence of a free radical generating
polymerization catalyst such as benzoyl peroxide. This latex is
then reacted with a polymerizable alkenyl-containing organic
material and a second graft link monomer. The latex particles of
the graft silicone-acrylate rubber hybrid may be separated from the
aqueous phase through coagulation (by treatment with a coagulant)
and dried to a fine powder to produce the silicone-acrylate rubber
impact modifier composition. This method can be generally used for
producing the silicone-acrylate impact modifier having a particle
size from about 100 nanometers to about two micrometers.
The thermoplastic composition may further comprise other
thermoplastic polymers, for example the rigid polymers as described
above without the elastomer modification, and/or the elastomers as
described above without the rigid polymeric grafts. Suitable rigid
thermoplastic polymers generally have a Tg greater than about
0.degree. C., preferably greater than about 20.degree. C., and
include, for example, polymers derived from monovinylaromatic
monomers containing condensed aromatic ring structures, such as
vinyl naphthalene, vinyl anthracene and the like, or monomers of
formula (9), for example styrene and alpha-methyl styrene;
monovinylic monomers such as itaconic acid, acrylamide,
N-substituted acrylamide or methacrylamide, maleic anhydride,
maleimide, N-alkyl, aryl or haloaryl substituted maleimide,
glycidyl (meth)acrylates; and monomers of the general formula (12),
for example acrylonitrile, methyl acrylate and methyl methacrylate;
and copolymers of the foregoing, for example styrene-acrylonitrile
(SAN), methyl methacrylate-acrylonitrile-styrene, and methyl
methacrylate-styrene. These additional thermoplastic polymers may
be present in amounts of up to about 50 wt. %, specifically about 1
to about 35 wt. %, more specifically about 10 to about 25 wt.
%.
In addition to the foregoing components, the polycarbonate
compositions further comprise a phosphorus containing flame
retardant, for example an organic phosphates and/or an organic
compound containing phosphorus-nitrogen bonds.
One type of exemplary organic phosphate is an aromatic phosphate of
the formula (GO).sub.3P.dbd.O, wherein each G is independently an
alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group, provided that
at least one G is an aromatic group. Two of the G groups may be
joined together to provide a cyclic group, for example, diphenyl
pentaerythritol diphosphate, which is described by Axelrod in U.S.
Pat. No. 4,154,775. Other suitable aromatic phosphates may be, for
example, phenyl bis(dodecyl)phosphate, phenyl
bis(neopentyl)phosphate, phenyl bis(3,5,5'-trimethylhexyl)
phosphate, ethyl diphenyl phosphate, 2-ethylhexyl
di(p-tolyl)phosphate, bis(2-ethylhexyl)p-tolyl phosphate, tritolyl
phosphate, bis(2-ethylhexyl) phenyl phosphate,
tri(nonylphenyl)phosphate, bis(dodecyl)p-tolyl phosphate, dibutyl
phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl
bis(2,5,5'-trimethylhexyl)phosphate, 2-ethylhexyl diphenyl
phosphate, or the like. A specific aromatic phosphate is one in
which each G is aromatic, for example, triphenyl phosphate,
tricresyl phosphate, isopropylated triphenyl phosphate, and the
like.
Di- or polyfunctional aromatic phosphorus-containing compounds are
also useful, for example, compounds of the formulas below:
##STR00013## wherein each G.sup.1 is independently a hydrocarbon
having 1 to about 30 carbon atoms; each G.sup.2 is independently a
hydrocarbon or hydrocarbonoxy having 1 to about 30 carbon atoms;
each X is independently a bromine or chlorine; m 0 to 4, and n is 1
to about 30. Examples of suitable di- or polyfunctional aromatic
phosphorus-containing compounds include resorcinol tetraphenyl
diphosphate (RDP), the bis(diphenyl)phosphate of hydroquinone and
the bis(diphenyl)phosphate of bisphenol-A (BPADP), respectively,
their oligomeric and polymeric counterparts, and the like. Methods
for the preparation of the aforementioned di- or polyfunctional
aromatic compounds are described in British Patent No.
2,043,083.
Exemplary suitable flame retardant compounds containing
phosphorus-nitrogen bonds include phosphonitrilic chloride,
phosphorus ester amides, phosphoric acid amides, phosphonic acid
amides, phosphinic acid amides, tris(aziridinyl)phosphine oxide.
The organic phosphorus-containing flame retardants are generally
present in amounts of about 0.1 to about 20 parts by weight, for
example, about 2 to about 18 parts by weight or about 4 to about 16
parts by weight, optionally about 2 to about 15 parts by weight,
based on 100 parts by weight of the total composition, exclusive of
any filler.
The thermoplastic composition may be essentially free of chlorine
and bromine, particularly chlorine and bromine flame retardants.
"Essentially free of chlorine and bromine" as used herein refers to
materials produced without the intentional addition of chlorine,
bromine, and/or chlorine or bromine containing materials. It is
understood however that in facilities that process multiple
products a certain amount of cross contamination can occur
resulting in bromine and/or chlorine levels typically on the parts
per million by weight scale. With this understanding it can be
readily appreciated that essentially free of bromine and chlorine
may be defined as having a bromine and/or chlorine content of less
than or equal to about 100 parts per million by weight (ppm), less
than or equal to about 75 ppm, or less than or equal to about 50
ppm. When this definition is applied to the fire retardant it is
based on the total weight of the fire retardant. When this
definition is applied to the thermoplastic composition it is based
on the total weight of polycarbonate, impact modifier and fire
retardant.
Optionally, inorganic flame retardants may also be used, for
example sulfonate salts such as potassium perfluorobutane sulfonate
(Rimar salt) and potassium diphenylsulfone sulfonate; salts formed
by reacting for example an alkali metal or alkaline earth metal
(preferably lithium, sodium, potassium, magnesium, calcium and
barium salts) and an inorganic acid complex salt, for example, an
oxo-anion, such as alkali metal and alkaline-earth metal salts of
carbonic acid, such as Na.sub.2CO.sub.3, K.sub.2CO.sub.3,
MgCO.sub.3, CaCO.sub.3, BaCO.sub.3, and BaCO.sub.3 or fluoro-anion
complex such as Li.sub.3AlF.sub.6, BaSiF.sub.6, KBF.sub.4,
K.sub.3AlF.sub.6, KAlF.sub.4, K.sub.2SiF.sub.6, and/or
Na.sub.3AlF.sub.6 or the like. When present, inorganic flame
retardant salts are generally present in amounts of about 0.01 to
about 1.0 parts by weight, more specifically about 0.05 to about
0.5 parts by weight, based on 100 parts by weight of polycarbonate
resin, impact modifier, polysiloxane-polycarbonate copolymer, and
phosphorus-containing flame retardant.
Anti-drip agents may also be included in the composition, and may
include, for example fluoropolymers, such as a fibril forming or
non-fibril forming fluoropolymer such as fibril forming
polytetrafluoroethylene (PTFE) or non-fibril forming
polytetrafluoroethylene, or the like; encapsulated fluoropolymers,
i.e., a fluoropolymer encapsulated in a polymer as the anti-drip
agent, such as a styrene-acrylonitrile copolymer encapsulated PTFE
(TSAN) or the like, or combinations comprising at least one of the
foregoing anti-drip agents. An encapsulated fluoropolymer may be
made by polymerizing the polymer in the presence of the
fluoropolymer. TSAN may be made by copolymerizing styrene and
acrylonitrile in the presence of an aqueous dispersion of PTFE.
TSAN may provide significant advantages over PTFE, in that TSAN may
be more readily dispersed in the composition. TSAN may, for
example, comprise about 50 wt. % PTFE and about 50 wt. %
styrene-acrylonitrile copolymer, based on the total weight of the
encapsulated fluoropolymer. The styrene-acrylonitrile copolymer
may, for example, be about 75 wt. % styrene and about 25 wt. %
acrylonitrile based on the total weight of the copolymer.
Alternatively, the fluoropolymer may be pre-blended in some manner
with a second polymer, such as for, example, an aromatic
polycarbonate resin or a styrene-acrylonitrile resin as in, for
example, U.S. Pat. Nos. 5,521,230 and 4,579,906 to form an
agglomerated material for use as an anti-drip agent. Either method
may be used to produce an encapsulated fluoropolymer. Anti-drip
agents are generally used in amounts of about 0.1 to about 1.4
parts by weight, based on 100 parts by weight of based on 100 parts
by weight of the total composition, exclusive of any filler.
In addition to the polycarbonate resin, the polycarbonate
composition may include various additives ordinarily incorporated
in resin compositions of this type. Mixtures of additives may be
used. Such additives may be mixed at a suitable time during the
mixing of the components for forming the composition.
Suitable fillers or reinforcing agents include, for example,
TiO.sub.2; fibers, such as asbestos, carbon fibers, or the like;
silicates and silica powders, such as aluminum silicate (mullite),
synthetic calcium silicate, zirconium silicate, fused silica,
crystalline silica graphite, natural silica sand, or the like;
boron powders such as boron-nitride powder, boron-silicate powders,
or the like; alumina; magnesium oxide (magnesia); calcium sulfate
(as its anhydride, dihydrate or trihydrate); calcium carbonates
such as chalk, limestone, marble, synthetic precipitated calcium
carbonates, or the like; talc, including fibrous, modular, needle
shaped, lamellar talc, or the like; wollastonite; surface-treated
wollastonite; glass spheres such as hollow and solid glass spheres,
silicate spheres, cenospheres, aluminosilicate (armospheres), or
the like; kaolin, including hard kaolin, soft kaolin, calcined
kaolin, kaolin comprising various coatings known in the art to
facilitate compatibility with the polymeric matrix resin, or the
like; single crystal fibers or "whiskers" such as silicon carbide,
alumina, boron carbide, iron, nickel, copper, or the like; glass
fibers, (including continuous and chopped fibers), such as E, A, C,
ECR, R, S, D, and NE glasses and quartz, or the like; sulfides such
as molybdenum sulfide, zinc sulfide or the like; barium compounds
such as barium titanate, barium ferrite, barium sulfate, heavy
spar, or the like; metals and metal oxides such as particulate or
fibrous aluminum, bronze, zinc, copper and nickel or the like;
flaked fillers such as glass flakes, flaked silicon carbide,
aluminum diboride, aluminum flakes, steel flakes or the like;
fibrous fillers, for example short inorganic fibers such as those
derived from blends comprising at least one of aluminum silicates,
aluminum oxides, magnesium oxides, and calcium sulfate hemihydrate
or the like; natural fillers and reinforcements, such as wood flour
obtained by pulverizing wood, fibrous products such as cellulose,
cotton, sisal, jute, starch, cork flour, lignin, ground nut shells,
corn, rice grain husks or the like; reinforcing organic fibrous
fillers formed from organic polymers capable of forming fibers such
as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene
sulfide), polyesters, polyethylene, aromatic polyamides, aromatic
polyimides, polyetherimides, polytetrafluoroethylene, acrylic
resins, poly(vinyl alcohol) or the like; as well as additional
fillers and reinforcing agents such as mica, clay, feldspar, flue
dust, fillite, quartz, quartzite, perlite, tripoli, diatomaceous
earth, carbon black, or the like, or combinations comprising at
least one of the foregoing fillers or reinforcing agents.
The fillers and reinforcing agents may be coated with a layer of
metallic material to facilitate conductivity, or surface treated
with silanes to improve adhesion and dispersion with the polymeric
matrix resin. In addition, the reinforcing fillers may be provided
in the form of monofilament or multifilament fibers and may be used
either alone or in combination with other types of fiber, through,
for example, co-weaving or core/sheath, side-by-side, orange-type
or matrix and fibril constructions, or by other methods known to
one skilled in the art of fiber manufacture. Suitable cowoven
structures include, for example, glass fiber-carbon fiber, carbon
fiber-aromatic polyimide (aramid) fiber, and aromatic polyimide
fiberglass fiber or the like. Fibrous fillers may be supplied in
the form of, for example, rovings, woven fibrous reinforcements,
such as 0-90 degree fabrics or the like; non-woven fibrous
reinforcements such as continuous strand mat, chopped strand mat,
tissues, papers and felts or the like; or three-dimensional
reinforcements such as braids. Fillers are generally used in
amounts of about 1 to about 50 parts by weight, based on 100 parts
by weight of the total composition.
Suitable heat stabilizers include, for example, organo phosphites
such as triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite,
tris-(mixed mono-and di-nonylphenyl)phosphite or the like;
phosphonates such as dimethylbenzene phosphonate or the like,
phosphates such as trimethyl phosphate, or the like, or
combinations comprising at least one of the foregoing heat
stabilizers. Heat stabilizers are generally used in amounts of
about 0.01 to about 0.5 parts by weight based on 100 parts by
weight of the total composition, excluding any filler.
Suitable antioxidants include, for example, organophosphites such
as tris(nonyl phenyl)phosphite,
tris(2,4-di-t-butylphenyl)phosphite,
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl
pentaerythritol diphosphite or the like; alkylated monophenols or
polyphenols; alkylated reaction products of polyphenols with
dienes, such as
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane,
or the like; butylated reaction products of para-cresol or
dicyclopentadiene; alkylated hydroquinones; hydroxylated
thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds;
esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid
with monohydric or polyhydric alcohols; esters of
beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with
monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl
compounds such as distearylthiopropionate, dilaurylthiopropionate,
ditridecylthiodipropionate,
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate
or the like; amides of
beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the
like, or combinations comprising at least one of the foregoing
antioxidants. Antioxidants are generally used in amounts of about
0.01 to about 0.5 parts by weight, based on 100 parts by weight of
the total composition, excluding any filler.
Suitable light stabilizers include, for example, benzotriazoles
such as 2-(2-hydroxy-5-methylphenyl)benzotriazole,
2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and
2-hydroxy-4-n-octoxy benzophenone or the like or combinations
comprising at least one of the foregoing light stabilizers. Light
stabilizers are generally used in amounts of about 0.1 to about 1.0
parts by weight, based on 100 parts by weight of polycarbonate
resin, impact modifier, polysiloxane-polycarbonate copolymer, and
phosphorus containing flame retardant.
Suitable plasticizers include, for example, phthalic acid esters
such as dioctyl-4,5-epoxy-hexahydrophthalate,
tris-(octoxycarbonylethyl)isocyanurate, tristearin, epoxidized
soybean oil or the like, or combinations comprising at least one of
the foregoing plasticizers. Plasticizers are generally used in
amounts of about 0.5 to about 3.0 parts by weight, based on 100
parts by weight of the total composition, excluding any filler.
Suitable antistatic agents include, for example, glycerol
monostearate, sodium stearyl sulfonate, sodium
dodecylbenzenesulfonate or the like, or combinations of the
foregoing antistatic agents. In one embodiment, carbon fibers,
carbon nanofibers, carbon nanotubes, carbon black, or any
combination of the foregoing may be used in a polymeric resin
containing chemical antistatic agents to render the composition
electrostatically dissipative. Antistatic agents are generally used
in amounts of about 0.1 to about 3.0 parts by weight based on 100
parts by weight the total composition, excluding any filler.
Suitable mold releasing agents include for example, stearyl
stearate, pentaerythritol tetrastearate, beeswax, montan wax,
paraffin wax, or the like, or combinations comprising at least one
of the foregoing mold release agents. Mold releasing agents are
generally used in amounts of about 0.1 to about 1.0 parts by
weight, based on 100 parts by weight of the total composition,
excluding any filler.
Suitable UV absorbers include for example, hydroxybenzophenones;
hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates;
oxanilides; benzoxazinones;
2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol
(CYASORB 5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB 531);
2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol
(CYASORB 1164); 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one)
(CYASORB UV-3638);
1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,-
3-diphenylacryloyl)oxy]methyl]propane (UVINUL 3030);
2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one);
1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenyl-
acryloyl)oxy]methyl]propane; nano-size inorganic materials such as
titanium oxide, cerium oxide, and zinc oxide, all with particle
size less than about 100 nanometers; or the like, or combinations
comprising at least one of the foregoing UV absorbers. UV absorbers
are generally used in amounts of about 0.01 to about 3.0 parts by
weight, based on 100 parts by weight based on 100 parts by weight
of polycarbonate resin, impact modifier, polysiloxane-polycarbonate
copolymer, and phosphorus containing flame retardant.
Suitable lubricants include for example, fatty acid esters such as
alkyl stearyl esters, e.g., methyl stearate or the like; mixtures
of methyl stearate and hydrophilic and hydrophobic surfactants
comprising polyethylene glycol polymers, polypropylene glycol
polymers, and copolymers thereof e.g., methyl stearate and
polyethylene-polypropylene glycol copolymers in a suitable solvent;
or combinations comprising at least one of the foregoing
lubricants. Lubricants are generally used in amounts of about 0.1
to about 5 parts by weight, based on 100 parts by weight of the
total composition, excluding any filler.
Suitable pigments include for example, inorganic pigments such as
metal oxides and mixed metal oxides such as zinc oxide, titanium
dioxides, iron oxides or the like; sulfides such as zinc sulfides,
or the like; aluminates; sodium sulfo-silicates; sulfates and
chromates; carbon blacks; zinc ferrites; ultramarine blue; Pigment
Brown 24; Pigment Red 101; Pigment Yellow 119; organic pigments
such as azos, di-azos, quinacridones, perylenes, naphthalene
tetracarboxylic acids, flavanthrones, isoindolinones,
tetrachloroisoindolinones, anthraquinones, anthanthrones,
dioxazines, phthalocyanines, and azo lakes; Pigment Blue 60,
Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179,
Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Green
7, Pigment Yellow 147 and Pigment Yellow 150, or combinations
comprising at least one of the foregoing pigments. Pigments are
generally used in amounts of about 1 to about 10 parts by weight,
based on 100 parts by weight based on 100 parts by weight of the
total composition, excluding any filler.
Suitable dyes include, for example, organic dyes such as coumarin
460 (blue), coumarin 6 (green), nile red or the like; lanthanide
complexes; hydrocarbon and substituted hydrocarbon dyes; polycyclic
aromatic hydrocarbons; scintillation dyes (preferably oxazoles and
oxadiazoles); aryl- or heteroaryl-substituted poly(2-8 olefins);
carbocyanine dyes; phthalocyanine dyes and pigments; oxazine dyes;
carbostyryl dyes; porphyrin dyes; acridine dyes; anthraquinone
dyes; arylmethane dyes; azo dyes; diazonium dyes; nitro dyes;
quinone imine dyes; tetrazolium dyes; thiazole dyes; perylene dyes,
perinone dyes; bis-benzoxazolylthiophene (BBOT); and xanthene dyes;
fluorophores such as anti-stokes shift dyes which absorb in the
near infrared wavelength and emit in the visible wavelength, or the
like; luminescent dyes such as
5-amino-9-diethyliminobenzo(a)phenoxazonium perchlorate;
7-amino-4-methylcarbostyryl; 7-amino-4-methylcoumarin;
3-(2'-benzimidazolyl)-7-N,N-diethylaminocoumarin;
3-(2'-benzothiazolyl)-7-diethylaminocoumarin;
2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole;
2-(4-biphenyl)-6-phenylbenzoxazole-1,3;
2,5-Bis-(4-biphenylyl)-1,3,4-oxadiazole;
2,5-bis-(4-biphenylyl)-oxazole;
4,4'-bis-(2-butyloctyloxy)-p-quaterphenyl;
p-bis(o-methylstyryl)-benzene; 5,9-diaminobenzo(a)phenoxazonium
perchlorate;
4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran;
1,1'-diethyl-2,2'-carbocyanine iodide;
3,3'-diethyl-4,4',5,5'-dibenzothiatricarbocyanine iodide;
7-diethylamino-4-methylcoumarin;
7-diethylamino-4-trifluoromethylcoumarin;
2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl;
7-ethylamino-6-methyl-4-trifluoromethylcoumarin;
7-ethylamino-4-trifluoromethylcoumarin; nile red; rhodamine 700;
oxazine 750; rhodamine 800; IR 125; IR 144; IR 140; IR 132; IR 26;
IR5; diphenylhexatriene; diphenylbutadiene; tetraphenylbutadiene;
naphthalene; anthracene; 9,10-diphenylanthracene; pyrene; chrysene;
rubrene; coronene; phenanthrene or the like, or combinations
comprising at least one of the foregoing dyes. Dyes are generally
used in amounts of about 0.1 to about 5 parts by weight, based on
100 parts by weight of the total composition, excluding any
filler.
Suitable colorants include, for example titanium dioxide,
anthraquinones, perylenes, perinones, indanthrones, quinacridones,
xanthenes, oxazines, oxazolines, thioxanthenes, indigoids,
thioindigoids, naphthalimides, cyanines, xanthenes, methines,
lactones, coumarins, bis-benzoxazolylthiophene (BBOT),
napthalenetetracarboxylic derivatives, monoazo and disazo pigments,
triarylmethanes, aminoketones, bis(styryl)biphenyl derivatives, and
the like, as well as combinations comprising at least one of the
foregoing colorants. Colorants are generally used in amounts of
about 0.1 to about 5 parts by weight, based on 100 parts by weight
of the total composition, excluding any filler.
Suitable blowing agents include for example, low boiling
halohydrocarbons and those that generate carbon dioxide; blowing
agents that are solid at room temperature and when heated to
temperatures higher than their decomposition temperature, generate
gases such as nitrogen, carbon dioxide, ammonia gas, such as
azodicarbonamide, metal salts of azodicarbonamide,
4,4'oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammonium
carbonate, or the like, or combinations comprising at least one of
the foregoing blowing agents. Blowing agents are generally used in
amounts of about 1 to about 20 parts by weight, based on 100 parts
by weight of the total composition, excluding any filler.
The thermoplastic compositions can be manufactured by methods known
in the art, for example in one embodiment, in one manner of
proceeding, powdered polycarbonate resin, impact modifier,
polydiorganosiloxane-polycarbonate copolymer, and/or other optional
components are first blended, optionally with chopped glass strands
or other filler in a Henschel high speed mixer. Other low shear
processes including but not limited to hand mixing may also
accomplish this blending. The blend is then fed into the throat of
a twin-screw extruder via a hopper. Alternatively, one or more of
the components may be incorporated into the composition by feeding
directly into the extruder at the throat and/or downstream through
a sidestuffer. Such additives may also be compounded into a
masterbatch with a desired polymeric resin and fed into the
extruder. The extruder is generally operated at a temperature
higher than that necessary to cause the composition to flow. The
extrudate is immediately quenched in a water batch and pelletized.
The pellets so prepared when cutting the extrudate may be
one-fourth inch long or less as desired. Such pellets may be used
for subsequent molding, shaping, or forming.
As noted above, it is particularly challenging to achieve excellent
flame retardancy while not adversely affecting the desirable
physical properties of the compositions, in particular impact
strength. It has been found by the inventors hereof that flame
retardant compositions having good physical properties and
excellent flame retardance in the absence of a brominated or
chlorinated flame retardant are obtained by careful balancing of
the relative amounts of the above-described polycarbonates, impact
modifiers, polysiloxane-polycarbonate copolymers, and organic
phosphorus-containing flame retardants. In particular, in one
embodiment, the thermoplastic composition comprises about 20 to
about 90 wt. % of the polycarbonate resin; about 1 to about 35 wt.
% of the impact modifier (when present); about 0.5 to about 30 wt.
% of the polysiloxane-polycarbonate copolymer; and about 0.1 to
about 20 wt. % of an organic phosphorus containing flame retarding
agent, each based on the total combined weight of the composition,
excluding any filler or other additive. Amounts outside of these
ranges result in compositions that have one or more of decreased
flame retardance; i.e., increased flame out time (FOT) or decreased
probability for passing, and/or decreased time to drip.
In various embodiments, samples of compositions described herein
having a thickness of 0.1 mm to 2.0 mm.+-.10%, e.g., 1.5 mm.+-.10%
or 1.2 mm.+-.10% achieve a UL94 5VB rating in the absence of a
brominated and/or chlorinated flame retardant. In some embodiments,
a sample of the thermoplastic composition having a thickness of 2.0
mm.+-.10% to 0.1 mm.+-.10%, when exposed to an open flame, has a
flame out time of less than 30 seconds in the absence of a
brominated and/or chlorinated flame retardant, optionally without
dripping. Underwriters Laboratories performs a periodic audit of
every polymer composition or grade which bears a UL flame rating. A
diagram of the UL Audit/Follow-up Services process is shown in FIG.
1. During an audit, five specimens of a polymer composition are
tested initially.
A retest of five additional specimens is allowed under certain
conditions amounting to a "near miss," that is, a single specimen
does not meet a single requirement for a pass rating. Specifically,
these conditions are: a single burn time exceeds the maximum burn
time value (V-0, 10 seconds; V-1, V-2, 30 seconds); or a sum of
individual burn times is greater than the maximum total burn time
allowed (V-0, 50 seconds; V-1, V-2 250 seconds) and is less than or
equal to the maximum retest total burn time value (V-0, 55 seconds,
V-1, V-2, 255 seconds); or a single specimen exhibits dripping
during the test.
Where a single specimen of a polymer composition fails to meet any
one of these conditions, a retest of a second set of specimens is
allowed. The polymer composition may pass the flame test on a
retest; the requirements listed in Table 1 are applied to retest
data. If a single specimen or the set of specimens fails to meet
more than one condition, no retest is allowed and a first submittal
failure occurs.
TABLE-US-00001 TABLE 1 Vertical Flame Class Requirements 94V-0
94V-1 94V-2 Individual burn time, seconds 10 30 30 Total burn time,
s (5 specimens .times. 2) 50 250 250 Glowing time, s (individual
specimen) 30 60 60 Drip particles that ignite cotton NO NO YES
Because the consequences of failing an audit are extremely serious,
UL Follow-up Services provides for submittal of a second set of
samples. On a second submittal, the second set of specimens is
tested exactly as a first set. Five specimens are tested initially,
with five additional specimens retested if the conditions are met
under which a retest is allowed (described above). The polymer
composition may pass the flame test on a second submittal, either
on testing the initial five specimens or on a retest. The
requirements listed in Table 1 are applied to second submittal
data.
Therefore, the data obtained from the UL-94 flame test may be in
the form of burn times for first and possibly second applications
of a flame to a single specimen, for first submission specimens
tested initially and retested, and for second submission specimens
tested initially and retested. Data relating to dripping of the
various specimens may also be considered. A statistical analysis of
data obtained from a flame tests on a number of samples (e.g., 20
or more) can be used to determine the probability of at least one
possible outcome of the UL test regimen. Possible outcomes include
a first submittal pass, including first time pass and retest, and a
second submittal pass, including first time pass and retest, and
failure. The probability of at least one outcome, preferably a
first time pass on a first submission, provides a measure of the
flame retardance of the polymer composition, while minimizing the
variability inherent in flame testing, particularly the UL-94
test.
The raw data may be transformed prior to use in the statistical
calculations by conversion to equivalent logarithmic values.
("Logarithm" and "logarithmic" refer to base 10 logarithms.) Times
less than one second may be rounded up to one second in order to
avoid negative logarithmic values. The logarithm of the burn time
may then be calculated and used in subsequent steps. Use of
transformed data is preferred as a more normal distribution of
values associated with burn time is thereby provided, as shown in
FIG. 2. Raw data do not show a normal (bell-shaped) distribution
curve because there can be no values less than zero, and data
points are typically clustered in the space below the maximum
individual burn time. The transformed data, however, more closely
fit a normal distribution curve, as shown in FIG. 2.
The probability of a first time pass on a first submission (pFTP)
may be determined according to the formula: pFTP=(P.sub.t1>mbt,
n=0.times.P.sub.t2>mbt,
n=0.times.P.sub.total<=mtbt.times.P.sub.drip, n=0) where
P.sub.t1>mbt, n=0 is the probability that no first burn time
exceeds a maximum burn time value, P.sub.t2>mbt, n=0 is the
probability that no second burn time exceeds a maximum burn time
value, P.sub.total<=mtbt is the probability that the sum of the
burn times is less than or equal to a maximum total burn time
value, and P.sub.drip, n=0 is the probability that no specimen
exhibits dripping during the flame test. First and second burn time
refer to burn times after a first and second application of the
flame, respectively.
The probability that no first burn time exceeds a maximum burn time
value, P.sub.t1>mbt, n=0, may be determined from the formula:
P.sub.t1>mbt, n=0=(1-P.sub.t1>mbt).sup.5 where
P.sub.t1>mbt is the area under the log normal distribution curve
for t1>mbt, and where the exponent "5" relates to the number of
bars tested.
The probability that no second burn time exceeds a maximum burn
time value may be determined from the formula: P.sub.t2>mbt,
n=0=(1-P.sub.t2>mbt).sup.5 where P.sub.t2>mbt is the area
under the normal distribution curve for t2>mbt. As above, the
mean and standard deviation of the burn time data set are used to
calculate the normal distribution curve. For the UL-94 V-0 rating,
the maximum burn time is 10 seconds. For a V-1 or V-2 rating the
maximum burn time is 30 seconds.
The probability P.sub.drip, n=0 that no specimen exhibits dripping
during the flame test is an attribute function, estimated by:
(1-P.sub.drip).sup.5 where P.sub.drip=(the number of bars that
drip/the number of bars tested).
The probability P.sub.total<=mtbt that the sum of the burn times
is less than or equal to a maximum total burn time value may be
determined from a normal distribution curve of simulated 5-bar
total burn times. The distribution may be generated from a Monte
Carlo simulation of 1000 sets of five bars using the distribution
for the burn time data determined above. Techniques for Monte Carlo
simulation are well known in the art. A normal distribution curve
for 5-bar total burn times may be generated using the mean and
standard deviation of the simulated 1000 sets. Therefore,
P.sub.total<=mtbt may be determined from the area under a log
normal distribution curve of a set of 1000 Monte Carlo simulated
5-bar total burn time for total<=maximum total burn time. For
the UL-94 V-0 rating, the maximum total burn time is 50 seconds.
For a V-1 or V-2 rating, the maximum total burn time is 250
seconds.
In particular embodiments, the composition has a flame out time of
less than 10 seconds, optionally with a probability of first time
pass (pFTP) of at least 0.85, the absence of a brominated and/or
chlorinated flame retardant.
In still other embodiments, a one-eighth inch (3.18 mm) (+3%) bar
comprising the composition has a notched Izod impact strength of at
least about 3.6 ft-lb/inch determined in accordance with ASTM D256
at room temperature, optionally greater than about 5.6 ft-lb/inch,
e.g., greater than or equal to about 6 ft-lb/inch.
A sample composition as described herein having a thickness of 2.5
mm (.+-.10%) may achieve a UL94 5VA rating in the absence of a
brominated and/or chlorinated flame retardant. In other
embodiments, a one-eighth inch (3.18 mm) (+3%) bar comprising the
composition has a notched Izod impact strength of at least about
3.6 ft-lb/inch determined in accordance with ASTM D256 at room
temperature.
In another embodiment, the thermoplastic composition comprises
about 40 to about 80 wt. % of the polycarbonate resin; about 2 to
about 15 wt. % of the impact modifier; more than 5 wt. % of the
polysiloxane-polycarbonate copolymer, e.g., about 10 to about 25
wt. %. Optionally, the composition may comprise 2 to 15 wt. % of an
organic phosphorus containing flame retarding agent, e.g., about 8
to 15 wt. %, based on the total combined weight of the composition,
excluding any filler. These amounts provide optimal flame
retardance, together with good notched Izod impact strength at
ambient temperature; good notched Izod impact strength at low
temperature; and/or good heat deflection temperature. In addition,
these amounts provide compositions that meet UL94 5VB, V0/V1 test
requirements and that meet other criteria such as minimum time to
drip, as described herein. Relative amounts of each component and
their respective composition may be determined by methods known to
those of ordinary skill in the art, for example, proton nuclear
magnetic resonance spectroscopy (.sup.1H NMR), ".sup.13C NMR, X-ray
fluorescence, high resolution mass spectroscopy, Fourier transform
infrared spectroscopy, gas chromatography-mass spectroscopy, and
the like.
In one embodiment, the thermoplastic compositions are of particular
utility in the manufacture flame retardant articles that pass the
UL94 vertical burn tests, in particular the UL94 5VB standard. In
the UL94 vertical burn test, a flame is applied to a vertically
fastened test specimen placed above a cotton wool pad. To achieve a
rating of 5VB, burning must stop within 60 seconds after five
applications of a flame to a test bar, and there can be no drips
that ignite the pad. Various embodiments of the compositions
described herein meet the UL94 5VB standard.
Thin articles present a particular challenge in the UL 94 tests,
because compositions suitable for the manufacture of thin articles
tend to have a higher flow. Thermoplastic compositions suitable for
the manufacture of a variety of articles will generally have a melt
volume rate (MVR) of about 4 to about 30 g/10 minutes measured at
260.degree. C./2.16 kg in accordance with ASTM D1238. Within this
range, for thin wall applications, the MVR may be adjusted to
greater than about 8, preferably greater than about 10, more
preferably greater than about 13 g/10 minutes, measured at
260.degree. C./2.16 kg in accordance with ASTM D1238.
Melt viscosity can provide an alternative indication flow.
Thermoplastic compositions as described herein suitable for the
manufacture of thin articles may have a melt viscosity at
260.degree. C./1500 sec.sup.-1 of about 50 to about 500
Pascal-second, measured in accordance with ISO 11443. In some
embodiments, the compositions meet the UL V2 criterion.
Flame retardance of the samples is excellent. It has been found
that in one embodiment, samples having a thicknesses of 1.2 and 2.0
mm (.+-.10%) pass the UL94 5VB standard. In addition, samples
having thicknesses of 1.2 mm or 1.5 mm perform well in a time to
drip test.
The thermoplastic compositions may further have a heat deflection
temperature (HDT) about 65.degree. C. to about 110.degree. C.,
specifically about 70.degree. C. to about 105.degree. C., measured
according to ISO 75/Ae at 1.8 MPa using 4 mm (.+-.3%) thick testing
bar.
The thermoplastic compositions may further have a Notched Izod
Impact (NoI) strength of about 3 to about 18 ft-lb/inch, or about 3
to about 14 ft-lb/inch, measured at room temperature using 1/8-inch
(3.18 mm) (.+-.3%) bars in accordance with ASTM D256.
The thermoplastic compositions may further have a Notched Izod
Impact (NU) strength of about 6 to about 18 ft-lb/inch, or about 6
to about 14 ft-lb/inch, measured at 10.degree. C. using 1/8-inch
(3.18 mm) (.+-.3%) bars in accordance with ASTM D256.
Shaped, formed, or molded articles comprising the thermoplastic
compositions are also provided. The thermoplastic compositions can
be molded into useful shaped articles by a variety of means such as
injection molding, extrusion, rotational molding, blow molding and
thermoforming to form articles such as, for example, computer and
business machine housings such as housings for monitors, hand held
electronic device housings such as housings for cell phones,
electrical connectors, and components of lighting fixtures,
ornaments, home appliances, roofs, greenhouses, sun rooms, swimming
pool enclosures, and the like. The above-described compositions are
of particular utility in the manufacture of articles comprising a
minimum wall thickness of as low as about 0.1 mm, 0.5 mm, 1.0 mm,
or 2.0 mm (about indicating .+-.10%). The above-described
compositions are also of particular utility in the manufacture of
articles comprising a minimum wall thickness of about 3 mm or less,
e.g., about 0.1 mm to about 2 mm, e.g., about 1.2 mm to about 2 mm,
or about 0.2 mm to about 1.8 mm or, more specifically, about 0.6 mm
to about 1.5 mm or about 0.8 mm to about 1.2 mm.
The present invention is further illustrated by the following
non-limiting examples. The following components were used:
TABLE-US-00002 TABLE 2 Component Type Source PC-1 BPA polycarbonate
resin made by a melt GE Plastics process with an MVR at 300.degree.
C./1.2 kg, of 23.5-28.5 g/10 min PC-2 BPA polycarbonate resin made
by a GE Plastics melt process with an MVR at 300.degree. C./ 1.2
kg, of 5.1-6.9 g/10 min PC-ST-1 Polysiloxane-polycarbonate
copolymer GE Plastics comprising units derived from BPA and units
derived from formula (10), wherein n is 0, R.sup.2 is propylene, R
is methyl, D has an average value of about 50, the copolymer having
an absolute weight average molecular weight of about 30000 g/mol,
and a dimethylsiloxane content of about 20 wt. % ABS-2 Bulk
polymerized ABS comprising GE Plastics 16% rubber and the balance
styrene/acrylonitrile BPA-DP Bisphenol A bis(diphenylphosphate)
NcendX P-30
In particular embodiments, the components shown in Table 2 (parts
by weight) and, in addition, 0.5 wt. % of a mold release agent and
0.25 wt. % of a combination of an antioxidant and a light
stabilizer, were blended to yield sample compositions in a Werner
& Pfleiderer co-rotating twin screw extruder (25 millimeter
screw) using a melt temperature range of about 260-280.degree. C.,
and subsequently molded at a temperature of 244.degree. C. for
impact and heat distortion temperature testing according to ASTM
standards 256 and 648 respectively on a Van Dorn 85HT injection
molding machine. Bars for flame testing were injection molded at a
temperature of 244.degree. C. on a Husky injection molding
machine.
Flammability tests were performed following the procedure of
Underwriter's Laboratory Bulletin 94 entitled "Tests for
Flammability of Plastic Materials, UL94." According to this
procedure, materials may be classified as HB, V0, UL94 V1, V2, 5VA,
and/or 5VB on the basis of the test results obtained for five
samples. The criteria for each of these flammability
classifications are described below and elsewhere herein.
V0: In a sample placed so that its long axis is 180 degrees to the
flame, the period of flaming and/or smoldering after removing the
igniting flame does not exceed ten seconds and the vertically
placed sample produces no drips of burning particles that ignite
absorbent cotton.
V1: In a sample placed so that its long axis is 180 degrees to the
flame, the period of flaming and/or smoldering after removing the
igniting flame does not exceed thirty seconds and the vertically
placed sample produces no drips of burning particles that ignite
absorbent cotton.
V2: In a sample placed so that its long axis is 180 degrees to the
flame, the average period of flaming and/or smoldering after
removing the igniting flame does not exceed twenty-five seconds,
but the vertically placed samples produce drips of burning
particles that ignite cotton. Five bar flame out time is the sum of
the flame out time for five bars, each lit twice for a maximum
flame out time of 250 seconds.
5VB: a flame is applied to a vertically fastened, 5-inch (127 mm)
by 0.5-inch (12.7 mm) test bar of a given thickness above a dry,
absorbent cotton pad located 12 inches (305 mm) below the bar. The
thickness of the test bar is determined by calipers with 0.1 mm
accuracy. The flame is a 5-inch (127 mm) flame with an inner blue
cone of 1.58 inches (40 mm). The flame is applied to the test bar
for 5 seconds so that the tip of the blue cone touches the lower
corner of the specimen. The flame is then removed for 5 seconds.
Application and removal of the flame is repeated for until the
specimen has had five applications of the same flame. After the
fifth application of the flame is removed, a timer (T-0) is started
and the time that the specimen continues to flame (after-flame
time), as well as any time the specimen continues to glow after the
after-flame goes out (after-glow time), is measured by stopping T-0
when the after-flame stops, unless there is an after-glow and then
T-0 is stopped when the after-glow stops. The combined after-flame
and after-glow time must be less than or equal to 60 seconds after
five applications of a flame to a test bar, and there may be no
drips that ignite the cotton pad. The test is repeated on 5
identical bar specimens. If there is a single specimen of the five
does not comply with the time and/or no-drip requirements then a
second set of 5 specimens are tested in the same fashion. All of
the specimens in the second set of 5 specimens must comply with the
requirements in order for material in the given thickness to
achieve the 5VB standard.
Time to drip: The time to drip is determined by alternately
applying and removing a flame as described for the 5VB test in
consecutive 5-second intervals, until the first drip of material
falls from the bar. A time to drip characteristic of 55 seconds (s)
or greater has been found to correlate well with other desired
characteristics such as 5VB ratings.
Flame retardance was also analyzed by calculation of the average
flame out time, standard deviation of the flame out time, as the
total number of drips, and using statistical methods to convert
that data to a prediction of the probability of first time pass, or
"pFTP", that a particular sample formulation would achieve a V0
"pass" rating in the conventional UL94 testing of 5 bars.
Preferably pFTP will be as close to 1 as possible, for example
greater than 0.9 and more preferably greater than 0.95, for maximum
flame-retardant performance in UL testing. A pFTP of 0.85 or
greater is deemed to be successful.
HDT was determined using a 4 mm thick (+10%) bar per ISO 75/Ae at
1.8 MPa.
MVR was determined at 260.degree. C. using a 2.16 kilogram load per
ASTM D1238.
NII was determined on one-eighth inch (3.18 mm) bars per ASTM D256
at room temperature (23.degree. C.).
Table 3 shows the UL94 flame performance using the vertical burning
5VB procedure, time to drip, and V-0/V-1 procedure for bars of
various diameters. The 5VB data represent the average of the flame
out times for each of ten bars for each sample composition. The
polycarbonate indicated in Table 3 is a 50/50 wt. % blend of the
PC-1 and PC-2 of Table 2. Flame out time (FOT) indicated in Table 3
for V0 and V1 tests is average from trials on each of twenty bars
for each sample composition, and the probability of each sample
passing on the first test (pFTP (probability of first time
pass)).
TABLE-US-00003 TABLE 3 Sample no. Components 1 2 3 4 5 6 7 8 9 10
11 Polycarbonate 73 53 73 63 53 70 65 50 89 69 69 PC-ST-1 5 25 5 15
25 5 10 25 5 25 18 ABS-2 10 10 10 10 10 9 9 9 2 2 2 BPADP 12 12 12
12 12 16 16 16 4 4 10 TSAN 0.5 0.5 1 1 1 1 1 1 1 1 1 Properties
"MVR, cm.sup.3/10 min" 17 13 15 10 9.3 26 21 17 7.7 4.7 17.2 "HDT,
.degree. C." 84.7 81.1 85 83.3 81.1 76.6 76.1 73 107.7 105.1 87.1
"NII, 23.degree. C., ft-lb/in" 5.6 11.7 5.6 11.5 16.8 3.5 6.1 11.5
11.2 19.2 14.7 5 VB (Flame Out Time) Tests and Time To Drip test at
indicated sample thickness FOT-2 mm 7 5.9 7.5 11.4 5.8 2.7 4.1 2.75
10 4 -- TTD-2 mm 55 71 61 73 84 71 77 96 52 87 -- FOT-1.5 mm 8.6
5.9 10.8 9.3 5.8 5.1 5.2 3.26 11 5 -- TTD-1.5 mm 27 57 47 74 77 41
61 75 47.3 83 -- FOT-1.2 mm 21 14 11 8.9 7.4 4.9 4.4 3.22 21 14 --
TTD-1.2 mm 42 52 43 52 57 47 60 67 41 51 V0/V1 Flame out Time (FOT)
Tests at indicated sample thickness (average of twenty tests on
twenty bars, with probability of first time pass (pFTP)) FOT-1.5 mm
1.67 1.43 2.5 3.3 1.8 0.8 1.1 0.8 3.4 1.1 -- pFTP-1.5 mm (V0) 0.77
0.91 0.64 0.6 0.9 0.97 0.9 1 0.45 0.94 -- pFTP-1.5 mm (V1) 1 1 1
0.99 1 1 1 1 0.71 0.99 -- FOT-1.0 mm 3.06 2.4 3.9 6.1 2.7 1.5 2.2
1.1 7 3.4 -- pFTP-1.0 mm (V0) 0.84 0.95 0.7 0.6 0.9 1 0.93 1 0.42
0.93 -- pFTP-1.0 mm (V1) 0.76 0.89 0.71 0.6 0.86 1 0.91 1 0.52 0.9
-- FOT-0.8 mm 8.3 8.5 8.2 9.84 8.5 3.4 3.9 3.1 11 9.2 2.3 pFTP-0.8
mm (V0) 0.4 0.43 0.5 0.57 0.64 0.75 0.79 0.89 0.22 0.36 0.97
pFTP-0.8 mm (V1) 0.43 0.6 0.49 0.46 0.85 0.59 0.53 0.99 0.4 0.52 1
FOT-0.5 mm -- -- -- -- -- -- -- -- -- -- 2.8 pFTP-0.5 mm (V1) -- --
-- -- -- -- -- -- -- -- 1 FOT-0.2 mm -- -- -- -- -- -- -- -- -- --
4.3 Legend: FOT - Flame out time (V0 - <10s; V1 - <30 s; 5 VB
- <60s) TTD - Time-to-drip (>55 s required)
The data of Table 3 reveals that compositions described herein
achieve different performance standards through different ranges of
proportions of ingredients. For example, a review of the data
pertaining to the time to drip test shows that adequate performance
can be achieved in samples 2mm thick with only a minor proportion,
e.g., 0.5 to 1 wt. % of the composition, polysiloxane-polycarbonate
copolymer with the use of an anti-drip additive (TSAN) as evidenced
by samples 1, 3 and 6, but increased amounts of TSAN do not lead to
adequate performance of thinner samples. The data of Table 3 shows,
however, that good time to drip performance for samples thinner
than 2 mm can be attained by including greater proportions of
polysiloxane-polycarbonate copolymer in the composition. FIG. 3
represents the results of Table 3 in this regard for samples
comprising 10.5 wt. % ABS-2 impact modifier, 10 wt. % BPADP and 1
wt. % TSAN for UL 5VB testing of 1.5 mm diameter samples, and shows
a generally direct correlation between time to drip performance and
the proportion of polysiloxane-polycarbonate copolymer in the
composition, i.e., that time to drip performance of samples thinner
than 2 mm improves as the proportion of polysiloxane-polycarbonate
copolymer increases. The data indicate that preferred results (time
to drip of 55 seconds or greater) will be attained with at least
about 7.5 wt. % the copolymer. FIG. 3 also shows that the
improvement in time to drip tapers off as the proportion of
polysiloxane-polycarbonate copolymer increases, so that little
appreciable improvement is seen when the proportion of the
copolymer is about 17.5 wt. % of the composition, or greater.
The data of Table 3 also shows that the effect of the proportion of
polysiloxane-polycarbonate copolymer copolymer in the composition
does not have a direct correlation with improved performance for
purposes of V0 testing, i.e., flame out time. Rather, as
represented in FIG. 4, the data for tests of samples of 1 mm
diameter comprising the same proportions of ABS-2, BPADP and TSAN
as the materials used for FIG. 3 indicates that flame out time is
at a maximum when polysiloxane-polycarbonate copolymer comprises
about 12.5 wt. % of the composition and that either greater or
lesser proportions of the copolymer give better results (see, e.g.,
samples 3, 4 and 5). Preferred flame out times, i.e., less than 10
seconds for V0 and, optionally, a probability of passing on the
first test 0.85 or better, are attained when the composition
comprises less than or equal to about 10.5 wt. % (see, e.g., sample
7), e.g., from about 7.5 to about 10.5 wt. %, but more than about
17.5 wt. % of the copolymer, e.g., from about 17.5 to about 25 wt.
% (see, e.g., samples 2, 5, 8, 10 and 11).
In still other embodiments, a combination of time to drip of at
least 55 seconds, flame out time of 60 seconds or less, optionally
30 seconds or less, e.g., 10 seconds or less, and Notched Izod
Impact (NH) performance of at least 3.6 fl-lb/in are desired, as
attained by samples 2, 4, 5, 8 and 10.
In some embodiments, desirable flame out time performance is
achieved irrespective of flame out time; for other embodiments,
time to drip performance is attained irrespective of flame out
time. In certain other embodiments, both flame out time and time to
drip performance may be attained. The data of Table 3 indicates
that embodiments that comprise about 7.5 to about 10.5 wt. %
polysiloxane-polycarbonate copolymer by weight can attain good
performance for both flame out time and time to drip. In another
example, a composition comprising polycarbonate,
polycarbonate-polysiloxane copolymer and an impact modifier as
described herein (designated sample 12) was tested with respect to
ultrasonic welding, with two comparative compositions designated
C-1 and C-2. The compositions were tested for melt viscosity, HDT
and NII. In addition, the compositions were molded into test parts
suitable for being joined by ultrasonic welding to form a
rectangular test article, as shown in the FIG. 5. Specifically,
each test article 10 comprised two parts 12, 14 designed to fit
together at mutually facing, longitudinally-aligned weld surfaces
16, 18 measuring 6 mm.times.13 mm to form a test article measuring
240 mm(l).times.12.7 mm(w).times.6 mm(t). The parts were welded
together using a Branson 400 series Ultrasonic Welding Machine
under the following conditions: frequency: 20 kHz (fix); pressure:
25 PSIG; weld time: 0.5 sec; hold time: 0.5 sec; booster amplitude
1:1 (standard); horn diameter 1.5 mm, flat face. The strength of
the welds were tested on a Shimazu Universal Testing machine in
which the ends of the test article were pulled apart at 5 mm/min.
The load at failure of the weld was noted. Flammability tests were
performed as well. The contents of the tested components and the
test results are set forth in the following Table 4:
TABLE-US-00004 TABLE 4 Components C-1* C-2* 12 Polycarbonate 99.09
86.03 71.54 Copolymer- 1 14 ABS-2 3 MBS
(Alkylmethacrylate-butadiene 3.98 copolymer) BPADP 8.97 10 PETS
0.35 0.3 0.3 Hindered Phenol AO 0.08 Phosphite Stabilizer 0.05 0.08
KSS (Potassium perfluorobutane 0.06 sulfonate) TSAN 0.5 0.67 1
Properties Ultrasonic weld load (kgf) 78 117 140 MVR, cm.sup.3/10
min 9 23 21 HDT, .degree. C. 127 93 89 NII, 23.degree. C., ft-lb/in
15 11 13 V0/Vl/V2 FOT-1.2 mm 2 1.5 pFTP-1.2 mm (V0) 0.95 1 FOT-0.8
mm 2.5 2.1 pFTP-0.8 mm (V0) 0.9 1 pFTP-0.8 mm (V1) 1 1 FOT-0.5 mm 5
2.7 pFTP-0.5 mm (V1) 1 pFTP-0.5 mm (V2) 0.99 1 FOT-0.2 mm 4.2
pFTP-0.2 mm (V2) 0.93
The data of Table 4 shows that a composition as described herein
not only exhibits advantageous flammability properties, it also
provides surprisingly superior ultrasonic weld seam strength
compared to a polycarbonate compositions not containing
polycarbonate-polysiloxane copolymer and impact modifier.
Therefore, a process of forming an article by ultrasonic welding at
least one part comprising the compositions described herein, and
the articles resulting therefrom, are also parts of this
invention.
The terms "first," "second," and the like, herein do not denote any
order, quantity, or importance, but rather are used to distinguish
one element from another, and the terms "a" and "an" and "the"
herein do not denote a limitation of quantity, but rather denote
the presence of at least one of the referenced item and may include
plural referents unless the context clearly dictates otherwise.
Compounds are described using standard nomenclature. For example,
any position not substituted by any indicated group is understood
to have its valency filled by a bond as indicated, or a hydrogen
atom. A dash ("-") that is not between two letters or symbols is
used to indicate a point of attachment for a substituent. For
example, --CHO is attached through carbon of the carbonyl group.
Unless defined otherwise, technical and scientific terms used
herein have the same meaning as is commonly understood by one of
skill in the art to which this invention belongs. The endpoints of
all ranges directed to the same property or amount are
independently combinable and inclusive of the endpoint. The
modifier "about" used in connection with a quantity is inclusive of
the stated value, and has the meaning dictated by the context, for
example the degree of error associated with measurement of the
particular quantity. Where a measurement is followed by the
notation "(.+-.10%)" or "(.+-.3%)", the measurement may vary within
the indicated percentage either positively or negatively. This
variance may be manifested in the sample as a whole (e.g., a sample
that has a uniform width that is within the indicated percentage of
the stated value), or by variation(s) within the sample (e.g., a
sample having a variable width, all such variations being within
the indicated percentage of the stated value). All references are
incorporated herein by reference.
While typical embodiments have been set forth for the purpose of
illustration, the foregoing descriptions should not be deemed to be
a limitation on the scope of the invention. Accordingly, various
modifications, adaptations, and alternatives may occur to one
skilled in the art without departing from the spirit and scope of
the present invention.
* * * * *